Azo sulphonamide compounds and method of producing the same



Patented Feb. 1, 1944- I 1120 SULPHONAMIDE COMPOUNDS AND METHOD OF PRODUCING THE SAME Max Dohrn, Berlin-Charlottenburg, and Paul Diedrich, Finkenkrug, Osthavclland, Germany, assignors to Schering Corporation, Bloomfield, N. 3., a corporation of New Jersey 'No Drawing Application December 21, 1937, Se- '1 rial No.- 180,942. In Germany December 30,

of acid character and a method of producingt-he same.-

"In German Patents Nos. 607,537, 610,320 and 638,701 compounds are already described in which o'nenucleus attached to the azo bridge possesses one sulphonic acid amide "groupin p-position or two such groups in any positions, while theother residue attached to the azo bridsemus't possess in addition to othergroupsa nuclearly bound nitrogen atom, which can form a member of a ring.

In accordance with the present invention, in the-flatter nucleus the presence of the specified nuclearly bound or cyclically bound nitrogen atom is not necessary for the production of highly bactericidal compounds. In fact'the compounds obtained according to the present process are distinguished by their particular bactericidal properties. In the present process as coupling components nitrogen free compounds of the naphthalene series, especially naphthol sulphonic acids, capable of coupling are employed.

As diazotised components with a sulphonic acid amide group the compounds described in' the above mentioned specifications arefsuitable such as 'para-aminobenzene sulphonamide; aminobenzene-sulphonalkylamides for example, the dimethylamide, and others.

The new compounds are distinguished by the high water-solubility of their salts and by .the neutrality of their solutions, because of which they appear to be particularly suitable for intravenous application.

. ,The following examples serve to. illustrate the invention without, however; limiting the same to them:

EXAMPLE 1 4 sulphonamido phenyl azo-1'42 hydromynaphthalene-6'-s-ulphonic acid 17.2 grams of 4-aminobenzene-sulphonamide are dissolved in 150 cos. of water and 25 cos. of hydrochloric acid and diazotised at C. with a solution of 6.9 grams of sodium nitrite, and coupled with ice cooling with a solution of 22.4 grams of 2.6-naphthol-sulphonic acid .containing excess of ammonia. The deep dark red solution thereby obtained is thereupon weakly acidified and; salted out with common salt. The dyestuff is easily water soluble. It can also be isolated by the addition of calcium chloride in the form of a difiicultly water-soluble calcium salt from the reaction solution.

EXAMPLE 2 4-suZphonamido-phenylazo-I'-(2'-hydroa:y-

naphthaZene-7'-sulphonic acid) 17.2 grams of -aminobenzene-sulphonamide are diazotised and coupled in solution alkaline 15 claims; (01. 260-200) The present invention relates to azo compounds with sodium carbonate with a solution of 24.6 grams of the sodium salt of ,2-naphthol-7-sulphonic acid. The solution is after filtration acidilied and the brown dysetuff precipitated by salting out.: The sulphonic acid filtered with Sue; tionis present inthe form ofits monosodium salt and is purified by washing with concentrated and. thereupon with 10% common salt solution. The yield amounts to about 60% of the theory.

EXAMPLE 3 4-sulphonamido-phenylazo l (2" -hydro-:cy-

naphthalene-'8'-sulphonic acid) 17.2 grams of diazotised l-aminobenzenesul-v phonamide are coupled, in solution alkaline with sodium carbonate, with an aqueous solution of 2%.6 grams or the sodium salt of 2-naphthol-8-' sulphonic acid, and according to the method de-' scribed in Example 2 the sodium salt of the sul phonic acid obtained as abrick red water-soluble powder. The yield amounts to 30 grams.

EXAMPLE 4 4-sulphonamido-phenylazo-2 (1 -hydro:ry-

naphthalme-Q-sulphonic acid) I EXAMPLE 5 4-sulphonamido-phenylazo-2'-(1'-hydromy naphthalene-5'-sulph;onic acid) 17.2 grams of diazotised 4-aminobenzene-sul-. phonamide are coupled, in solution alkaline with sodium carbonate, with a solution of 24.6 grams or the sodium salt of 1-naphthol-5-sulphonic acid. The customary working up yields the azo-dyestuff as a dark red sodium salt which is easily soluble in water.

EXAMPLE 6 4-sulphonamido-phenylazo-1'-(2'-hydromynaphthalene-3.6'-disulphonic acid) 17.2 grams of diazotised 4-aminobenzene-sul phonamide are coupled with ice cooling, in solu-- tion alkaline with sodium carbonate, with an. aqueous solution of 34.8 grams of the sodium salt. of 2-naphthol-3.6-disulphonic acid. By acidifi-- cation and salting out, the coupling product is. obtained as a cinnabar red powder. It is the disodium salt of the azo dyestufl and as such easily soluble in water. The yield amounts to iograms.

EXAMPLE 7 4 -sulphonamido-phenylazo-I (2 -hydro:cynaphthaZene-6'.8'-disulphonic acid) By coupling of a solution of 17.2 grams of di- .1

azotised 4-aminobenzene-sulphonamide and, a.

solution of 34.8 grams of thesodium salt. of, 2-K

naphthol-6.8-disulphonic acid, after the customary working up, the disodium salt of the azo dyestufi' is obtained in orange red needles. The yield amounts to 38 grams.

EXAMPLE 8 4-suZphonamido-phenylazo-2'-(1-hydromy naphthalene-3'.6'-disulphonic acid) 17.2 grams of diazotised 4-aminobenzene-sulphonamide coupled with 34.8 grams of the some salt of l-naphthol-3.6-disulphonic acid, yield according to the method of working of Example '7, 35 grams of the disodium salt of the dyestufi. The light red product is easily soluble in water,

EXAMPLE Y 9 4sulphonamide-phenylazo-2 (1 -hydroxynaphthalene-3'.8'-disulphonic acid) The disodium salt of this acid is obtained as described in Example 8 except that the sodium salt of 1-naphthol-3.8 disulphonic acid is employed instead of the sodiumsalt of l-naphthol- 3.6-disulphonic acid, the product being a darkred easily water-soluble powder. The yield amounts to 32 grams. 1

EXAMPLE 10 4-sulphonamido-phenylazo-2' (1 -hydroa:ynaphthalene-4'.8'-disulphonic acid) I with the acid aromatic components, even if these processes possess less practical importance. Thus also the azo bridge or the sulphonic acid amide group can be produced in the last phase or also the acid group can be introduced into the arc-- matic residue after the manufacture of the azo compound. For this purpose processes come into question as correspond to the processes set forth inhGerman specifications Nos. 607,531-610,320 and 638,701. The above alternative processes are to be considered as chemical equivalents' of the coupling process.

Of course, many changes land'variations in the reaction conditions and the like may be employed by those skilled in the art in accordance with the principles set forth herein and in the claims annexed hereto.

What we claim is:

1. Process for the manufacture of azo compounds of acid character, comprising coupling a diazo benzene having asulphonamide group lin the para-position to theazo; group, with ;a:nitrogen-free naphthol sulphonic acid. a 1

2. Process according to claim 1, wherein paraaminobenze'ne-sulphonamide is diazotised and coupled with a 2-naphthol-sulphonic acid.

' 3. Process as claimed in claim 1, in which a 4- aminobenzene-sulphonamide is diazotised and coupled with a 2,8-naphthol-sulphonic acid.

4. Process as claimed in claim 1, in which a 4- aminobenzene-sulphonamide is diazotised and coupled with 2,6enaphthol-sulphonic acid.

5. Process as'olaimed in claim 1, in which a 4- aminobenzene-sulphonamide is diazotised and coupled; with 2naph thol-6,8-disulphonic acid.

' d'roxynaphthalene sulphonic acid).

10. P sulphonamide benzene azo naphthol. sulphonic acids.

11. A 4,esulphonamldephenylazo 1' (z ny.- droxynaphthale'neeii' sulphonic acid) compound of the general formula cl n osmsz. and the structuralv formula I N=NO 0mm.

12. A l sulphonamidephenylazo -'1' (2' -hym' na htha 'rs a d) c o nd of the general formula o l-moms; and 'the structural formula i '5 Boss N=NOSO2NH2 13. A 4 sulphonamidephen ylazo 1"- (2 --hydroxynaphthalene-Gfifi'-'disulphonicacid) compound of the general formula C16H1309N3S3 and the structural formula Hols N= Os 0mm 14. A composition prepared-for administration into .the human .organismand comprising. a. .p.-. sulphonamide benzene-azo -naphthol-isulphonicacid;'..: 1

15.; A compositionprepared for administration 111170, the human organism and comprising a. p, u Dh Lamiderbenzene-azo-naphthol-disulphonic 8;Cid. r I

X DoHRN. PAUL DIEDRICH. 

